CN101445250A - Organic matter/mineral complex and preparation method thereof - Google Patents
Organic matter/mineral complex and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of remediation of heavy metal polluted soil by in situ passivation, particularly to an organic matter/mineral complex and a preparation method thereof. In the complex, the mineral is sodium bentonite, and the organic matter is pig manure and degradation liquid thereof; the solvent includes hydrochloric acid, sodium hydroxide, copper sulfate and silver nitrate; and the weight ratio of the organic matter and the mineral is 1:(1-6). The preparation method comprises the steps of adding water-wetted dry pig manure into effective microorganism (EM) liquid, culturing at 25DEG C for 30 days, centrifuging, collecting supernatant, filtering to obtain degradation liquid, adding buffered degradation liquid into slurry form sodium bentonite, preparing into 10% suspension, adjusting pH value to 3-11, allowing reaction under controlled temperature for 0.5-3 h, cooling, centrifuging, collecting sediment, and air-drying. The complex has the advantages of simple principle, safe and feasible preparation method, stable product properties, and good usability; and can be widely used for remediation of various kinds of soil by passivation.
Description
Technical field:
The present invention relates to be used for a kind of organism in in-situ passivation recovery technique field of heavy-metal contaminated soil occasion and mineral complex and preparation method thereof.
Background technology:
At present, the soil in the agricultural land is because life-time service chemical fertilizer and various agricultural chemicals, and the pollution of adding water quality makes the heavy metal content complexity in the soil, influenced the agriculture performance and the quality of soil.For a long time, the in-situ passivation technology of seeking a kind of rehabilitating soil more and more causes relevant department and expert's attention, particularly seek a kind of organism and inorganics combination of utilizing, realize soil in-situ passivation repairing effect, more help the raising and the agricultural development of China's soil quality.
Wilkinite (Bentonite) normally with numerous mineral associations, be the clay pit inorganics of main component with montmorillonite (Montmorillonite).The characteristic of montmorillonite has determined bentonitic fundamental property, and it is the 2:1 type layer silicate mineral that is sandwiched in the octahedra formation of aluminium (magnesium) oxygen (hydroxyl) therebetween by two-layer tetrahedral si-o film and one deck, belongs to oblique system.Pig manure is as organism, and the main chemical compositions of its degraded product is an organic acid, as humic acid, fulvic acid, amino acid, and perhaps carbohydrate and nitrogenous, sulfurheterocyclic compound etc., their active group has: COO-,-NH ,=NH ,=PO
4,-S-,-O-etc.
The geometric space of structure cell sheet interlayer has constituted unique montmorillonite interlamination region, and this is a special chemical reaction place.By physico-chemical process such as interlayer exchange, interlayer absorption, interlayer catalysis, interlayer polymerization, interlayer be pillared, other ion or compound are introduced the montmorillonite interlamination region, change electric charge, medium, the interlamellar spacing of its interlamination region, breakable layer charge distribution balance, make its structure and properties that corresponding the variation be taken place, just can make the novel material of different performance.The laminate structure of montmorillonite and strong ion-exchange capacity make superpolymer possibility intercalation reach the combination of molecular level between the montmorillonite lamella.At normal temperatures and pressures, ion, water and salt and nearly all organism can both pass in and out the interlayer of montmorillonite mineral, form complicated montmorillonite inorganic complex or montmorillonite organic complex.
The key influence factor of preparation organic and inorganic complex body mainly contains former soil structure, organic kind, preparation technology etc.The preparation technology of organic compound directly influences quality product between montmorillonite layer.Behind definite montmorillonite raw material, organic materials, the key link of preparation is organic add-on, reaction environment (comprising system pH, temperature, reaction times etc.).People such as Han Lirong studies show that, the properties-correcting agent consumption is the principal element that influences the organobentonite absorption property.People such as Chen Defang studies show that, the bonding force of organobentonite interlayer planar water a little less than, its thermotolerance is relevant with the organic carbon chain length, carbochain is long more, decomposition temperature is high more.Tong Zhangfa etc. have studied Ningming, Guangxi The Purification of Swelled-ground, sodium in great detail, have organised, and have prepared high performance organobentonite.Be used for soil passivation recovery technique but at present organism such as inorganics such as wilkinite and pig manure are made complex body, also Shang Weijian has the report of success.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seeking to design a kind of is raw material with sodium bentonite and pig manure, adopts the wet processing preparation to meet the organic and inorganic complex body of anchored in place technology; Change four major influence factors such as add-on, reaction times, system pH and temperature of reaction of organism pig manure degradation solution respectively by the experiment of single factor method, determine the best technology of preparing parameter of organic-inorganic complex; And the surface property of organic and inorganic complex body of preparation analyzed, for the actual production of commercialization organic and inorganic complex body provides technical scheme.
To achieve these goals, the employed inorganics wilkinite of the complex body that the present invention relates to is a sodium bentonite, and its cation exchange capacity (CEC) is 60mmol/100g, and expansion multiple is 15ml/g, and colloid index is 100ml/15g; Organism is pig manure and degradation solution thereof; Reagent comprises hydrochloric acid, sodium hydroxide, copper sulfate and Silver Nitrate; Complex body prepares that organism and inorganics weight proportion are 1:1～6 in the process.
Realization equipment used of the present invention comprises acidometer, magnetic force heating stirrer, electronic balance, electric centrifuge, micro-electrophoresis apparatus, atomic absorption spectrophotometer and scanning electron microscope; Its technology comprises the preparation of pig manure degradation solution and two steps of organic-inorganic complex body preparation:
(1) pig manure degradation solution preparation
The part by weight of getting dried pig manure: water=1:25 is packed in the container, under 25 ℃ of constant temperatures, add EM bacterium liquid and cultivated 30 days, centrifugal 10 minutes of culture (4000r/min), supernatant liquor filters with the middling speed quantitative paper, and filtrate is that the pig manure degradation solution places 4 ℃ of environment under preservation standby;
(2) organic and inorganic complex body preparation
The suspension wet processing is adopted in organic and inorganic complex body preparation, and at normal temperatures and pressures, ion, water and salt and organism can both pass in and out the interlayer of montmorillonite mineral, form complicated montmorillonite inorganic complex and montmorillonite organic complex.
Get the sodium bentonite breeze of 100 order fineness, add water and be stirred to pulpous state, slowly add standby pig manure degradation solution again, the suspension that is made into 10% weight percent concentration reacts, pH value with 1.0mol/L sodium hydroxide or 1.0mol/L hydrochloric acid soln regulation system is 3～11, after reacting 0.5～3 hour under 25～70 ℃ of temperature, be cooled to room temperature, the unreacted organism of water flush away, with till the Silver Nitrate check nothing precipitation, centrifugal sediment grinds behind the natural air drying at normal temperatures, crosses 100 mesh sieves again, obtain the organic and inorganic complex body, it is standby to put into the moisture eliminator inner drying.
(3) each analysis of influential factors: getting institute's aglycon amount concentration is 40mg/L (C
0, Cu mg/L)
2+Each 25ml of water sample is put in respectively in a plurality of Erlenmeyer flasks, successively to wherein adding the organic and inorganic complex body 0.5g that makes under the different experimental conditions respectively, and 25 ℃ of constant temperature vibration 30min, the centrifugal 15min of 4000r/min gets its supernatant liquid, measures its Cu
2+Concentration (C
e, mg/L), 1. calculate Cu in the simulated water sample with formula
2+Clearance (η, %).Cu
2+The concentration atomic absorption spectrophotometer; The measuring method of Zeta potential; Organic and inorganic complex structure pattern adopts the S570 of Hitachi type scanning electron microscope to measure.Calculate Cu
2+Clearance (η, formula %) is:
Ce: after the adsorption equilibrium, Cu in the solution
2+Concentration, mg/L;
C
0: before the absorption, Cu in the solution
2+Concentration, mg/L.
It is inorganic raw material that the present invention adopts resourceful mineral substance sodium bentonite, with the pig manure is organic raw material, be prepared into the organic and inorganic complex body through the suspension wet method, be applied to repair the in-situ techniques of agricultural soil, realize soil in-situ passivation repairing effect, its principle is simple, preparation technology's safe and feasible, the complex performance of preparation is stable, and usability is good, can be widely used in the passivation reparation of various soil.
Embodiment:
Below by embodiment the present invention is further described.
Embodiment 1: the weight proportion that changes pig manure and sodium bentonite prepares complex body respectively.
Prepare technology and employed equipment carries out the complex body preparation according to the preparation technology of pig manure degradation solution and organic-inorganic complex body, choose system pH=7,25 ℃ of room temperatures, churning time is under the 2.5h condition, each weight proportion that only changes pig manure, sodium bentonite is respectively 1:6,1:5,1:4,1:3,1:2 or 1:1, it is compound to carry out organic and inorganic, and the product that obtains is with to heavy metal Cu
2+Eliminating rate of absorption be the weight proportion of the best pig manure of standard determination, sodium bentonite, the result shows: along with pig manure, sodium bentonite weight proportion increase gradually, the organic and inorganic complex body that makes is to Cu
2+Clearance also increase gradually; And at pig manure: during sodium bentonite 〉=1:3, the organic and inorganic complex body is to Cu
2+Clearance tend to balance, clearance reaches 96.89%, i.e. pig manure: best results when sodium bentonite is 1:3.
Embodiment 2: the change reaction times prepares complex body respectively.
Prepare technology according to the preparation technology of pig manure degradation solution and organic and inorganic complex body and be prepared complex body, select dried pig manure: sodium bentonite=1:3, reaction system pH=7, temperature of reaction is 25 ℃, change the reaction times respectively and be 0.5,1,1.5,2,2.5 or 3h, it is compound to carry out organic and inorganic, and the product that obtains is with to heavy metal Cu
2+Eliminating rate of absorption be the standard determination optimum reacting time; Its result shows: along with the growth of organic and inorganic complex reaction time, the organic and inorganic complex body of preparation is to heavy metal Cu
2+Eliminating rate of absorption increase gradually, and the reaction 2.5 hours, clearance tends to balance constant, clearance reaches 96.41%, promptly selecting 2.5 little the reaction times is best preparation time.
Embodiment 3: the pH that changes reaction system prepares complex body respectively.
Prepare technology according to the preparation technology of pig manure degradation solution and organic-inorganic complex body and be prepared complex body, 25 ℃ of room temperatures, churning time is 2.5h, pig manure: sodium bentonite=1:3, with sodium hydroxide and hydrochloric acid respectively the pH of regulation system be 3,5,7,9 or 11, it is compound to carry out organic and inorganic respectively, and the product that obtains is with to heavy metal Cu
2+Eliminating rate of absorption be standard determination best complex system pH, its result shows: when system was in neutrality or meta-alkalescence, the organic and inorganic complex body of preparation was to Cu
2+Clearance the highest, this is that the positively charged ion with comparatively large vol is entered interlayer repulsive interaction because montmorillonite its surface in acidic aqueous media is positively charged, hinders the cationic exchange effect; Under the highly basic condition, also be unfavorable for the compound effect of organic-inorganic, may be-reason of OH and organic molecule competitive adsorption; And under neutrality or meta-alkalescence condition, not having this repulsive interaction, the organic ion and the polar molecule that enter interlayer can increase.Therefore, between the pH value of preparation feedback system is controlled at 6～8 for well.
Embodiment 4: change temperature of reaction and carry out the complex body preparation respectively.
Prepare technology according to the preparation technology of pig manure degradation solution and organic-inorganic complex body and be prepared complex body, in the heated and stirred time is 2.5h, pig manure: sodium bentonite=1:3, pH is controlled under 6～8 conditions, changing temperature of reaction respectively is 25,40,50,60 or 70 ℃, it is compound to carry out organic and inorganic, and the product that obtains is with to heavy metal Cu
2+Eliminating rate of absorption be the standard determination optimal reaction temperature, its result shows: the organic and inorganic complex body is to Cu
2+Clearance and preparation temperature be not linear dependence; Along with the preparation feedback temperature raises, the organic and inorganic complex body is to Cu between 25 ℃ ~ 60 ℃
2+Clearance raise, when preparation feedback temperature during greater than 60 ℃, the organic and inorganic complex body is to Cu
2+Clearance tend to balance, clearance reaches 96.76%.Therefore, the preparation feedback temperature is controlled at 60 ℃ for well.
The surface property of the organic and inorganic complex body of present embodiment preparation is as follows:
(1) surface charge Zeta potential
Sodium bentonite and organic and inorganic complex body are scattered in respectively in the water, adopt the Zeta potential in the micro-electrophoresis apparatus mensuration solution, characterize its surface charging situation; After measured, sodium bentonite original soil surface is electronegative, and current potential is-48.0mV; Because it is that water conditioner is removed water pollutant four big mechanism are arranged that charge neutrality, adsorption bridging, compression double electric layer and net sweep that volume catches.In these four mechanism, charge neutrality accounts for critical role, fixing agent surface electrically charged be the major influence factors of charge neutrality effect.Wilkinite is as the electrically charged ability that affects the removal heavy metal of a kind of fixing agent surface institute, and permanent negative charge is with on the wilkinite surface, and heavy metal cation is positively charged, helps adsorbing heavy metal cation.Though it is electronegative to record the organic and inorganic complex surfaces, current potential is-38.7mV that more former wilkinite has raise.The raising of Zeta potential in theory illustrates the electronegative minimizing in surface, and the charge neutrality ability reduces, and is unfavorable for improving it to cationic absorption.
(2) surface scan Electronic Speculum
Transmission scanning electron microscope display result under sodium bentonite and the organic and inorganic complex body different amplification shows: sodium bentonite and the pattern of organic and inorganic complex body under different amplification, both have all presented aggregating state, the pattern of the compound and sodium bentonite of organism pig manure degradation solution is compared, the original soil particle is tight, the organic and inorganic complex body is more loose, and the surface is more coarse, helps its Adsorption of Heavy Metal Ions.
(3) the best technology of preparing parameter of present embodiment is: be made into 10% suspension with the pig manure degradation solution, and pig manure: sodium bentonite=1:3, the pH value of reaction system is 6～8, and temperature of reaction is 60 ℃, and the stirring reaction time is 2.5 hours; Organic and inorganic complex surfaces negative charge according to best technology of preparing parameter preparation raises than original soil; The more former soil loosening of particle, coarse helps its Adsorption of Heavy Metal Ions.
Claims (2)
1, a kind of organism and mineral complex is characterized in that the employed inorganics of complex body is a sodium bentonite, and its cation exchange capacity (CEC) is 60mmol/100g, and expansion multiple is 15ml/g, and colloid index is 100ml/15g; Organism is pig manure and degradation solution thereof; Reagent comprises hydrochloric acid, sodium hydroxide, copper sulfate and Silver Nitrate; Complex body prepares that organism and inorganics weight proportion are 1:1～6 in the process.
2, the preparation method of a kind of organism and mineral complex, it is characterized in that comprising the preparation of pig manure degradation solution and two steps of organic-inorganic complex body preparation: the one, the preparation of pig manure degradation solution, the part by weight of getting dried pig manure: water=1:25 is packed in the container, under 25 ℃ of constant temperatures, adding EM bacterium liquid cultivated 30 days, with centrifugal 10 minutes of culture, supernatant liquor filtered with the middling speed quantitative paper, and filtrate is that the pig manure degradation solution places 4 ℃ of environment under preservation standby; The 2nd, the preparation of organic and inorganic complex body, get the sodium bentonite breeze of 100 order fineness, add water and be stirred to pulpous state, slowly add standby pig manure degradation solution again, the suspension that is made into 10% weight percent concentration reacts, pH value with 1.0mol/L sodium hydroxide or 1.0mol/L hydrochloric acid soln regulation system is 3～11, after reacting 0.5～3 hour under 25～70 ℃ of temperature, be cooled to room temperature, the unreacted organism of water flush away is again with till the Silver Nitrate check nothing precipitation, centrifugal sediment grinds behind the natural air drying at normal temperatures, cross 100 mesh sieves, obtain the organic and inorganic complex body, it is standby to put into the moisture eliminator inner drying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059098A (en) * | 2010-11-24 | 2011-05-18 | 天津师范大学 | Method for preparing montmorillonite-humic acid compound under alkaline condition |
| CN103788959A (en) * | 2014-03-03 | 2014-05-14 | 江南大学 | Heavy metal contaminated soil remediation agent and preparing method thereof |
| CN104117529A (en) * | 2014-07-09 | 2014-10-29 | 华南师范大学 | In-situ remediation method of acidic soil containing heavy metals |
| CN105084402A (en) * | 2015-08-11 | 2015-11-25 | 广西大学 | Stable and harmless treatment technology for residual heavy metal in livestock excrement |
| CN110711768A (en) * | 2019-10-18 | 2020-01-21 | 国家林业和草原局竹子研究开发中心 | Organic-inorganic complex generated by catalytic cracking of clay minerals and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219536A (en) * | 1990-07-16 | 1993-06-15 | Board Of Trustees Operating Michigan State University | Composite clay materials for removal of sox from gas streams |
| CN100467119C (en) * | 2006-11-20 | 2009-03-11 | 暨南大学 | Preparing process for organic modified bentonite composite material |
| CN100429146C (en) * | 2006-11-27 | 2008-10-29 | 浙江大学 | Method for synthesizing composite material of organic - inorganic bentonite |
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2008
- 2008-12-05 CN CN2008102381981A patent/CN101445250B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059098A (en) * | 2010-11-24 | 2011-05-18 | 天津师范大学 | Method for preparing montmorillonite-humic acid compound under alkaline condition |
| CN103788959A (en) * | 2014-03-03 | 2014-05-14 | 江南大学 | Heavy metal contaminated soil remediation agent and preparing method thereof |
| CN103788959B (en) * | 2014-03-03 | 2016-06-22 | 江南大学 | A kind of heavy-metal contaminated soil renovation agent and preparation method thereof |
| CN104117529A (en) * | 2014-07-09 | 2014-10-29 | 华南师范大学 | In-situ remediation method of acidic soil containing heavy metals |
| CN104117529B (en) * | 2014-07-09 | 2016-03-23 | 华南师范大学 | A kind of in-situ remediation method containing heavy metal acid ground |
| CN105084402A (en) * | 2015-08-11 | 2015-11-25 | 广西大学 | Stable and harmless treatment technology for residual heavy metal in livestock excrement |
| CN110711768A (en) * | 2019-10-18 | 2020-01-21 | 国家林业和草原局竹子研究开发中心 | Organic-inorganic complex generated by catalytic cracking of clay minerals and application thereof |
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